Polyurethane polymers characterized by lactone groups and hydroxyl groups in the polymer backbone

Abstract

Polyurethane polymers characterized by a molecular weight above 6,000 and having lactone groups and hydroxyl groups in the polymer backbone are prepared by reacting a mixture of polyglycols proportioned so as to provide the desired polymer properties, a polyfunctional lactone and a polyfunctional isocyanate. The product is soluble in alkaline solutions and may be used for light sensitive photographic layers on films, paper or glass; in drug delivery systems, as burn dressings, in body implants such as vascular prosthesis, and in the manufacture of catheters. The novel polymers also find use in the manufacture of artificial finger nails, finger cots, adhesives, and in protective and hydrostatic drag resistant coatings. The water absorptivity of the polyurethane lactone polymers is above 10%, preferably above 20%, and these polymers may range to completely gel-like high water absorptive polymers. The polymers of the present invention can provide a leachable substrate wherein the leaching agent may be water, gases, alcohols, esters and body fluids, e.g., animal or human.

What is claimed is: 
     
       1. A polyurethane polyether resin having lactone groups in the polymer backbone. 
     
     
       2. The polyurethane polyether resin of claim 1 having hydroxyl groups in the polymer backbone. 
     
     
       3. A polyurethane polyether resin characterized by a molecular weight above 6000 and having lactone groups in the polymer backbone, said urethane polymer comprising the reaction product of: (a) a polyfunctional lactone selected from the group consisting of (1) lactones having the formula: ##STR2## wherein R 1  is a monovalent radical selected from the group consisting of --H, --CHNH 2 , --SO 2  CH 3 , --CHOHCOOH, and --(CHOH) n  CH 2  OH; n being an integer from 0 to 5; and R 2  is a divalent radical --(CHOH) m  --; m being an integer from 3 to 10 and (2) D-glucuronolactone;   (b) a polyalkylene oxide glycol; and   (c) an organic polyisocyanate; said urethane polymer being soluble in alkaline solutions.     
     
     
       4. The polyurethane polyether resin of claim 3 wherein said lactone is delta gluconolactone. 
     
     
       5. The polyurethane polyether resin of claim 3 wherein said lactone is mannolactone. 
     
     
       6. The polyurethane polyether resin of claim 3 wherein said lactone is sorbolactone. 
     
     
       7. The polyurethane polyether resin of claim 3 wherein said lactone is D-glucuronolactone. 
     
     
       8. The polyurethane polyether resin of claim 3 wherein said polyalkylene oxide is polyethylene glycol having a molecular weight of 1450. 
     
     
       9. The polyurethane polyether resin of claim 3 wherein said polyalkylene oxide glycol is a mixture of polyethylene glycol and diethylene glycol. 
     
     
       10. The polyurethane polyether resin of claim 3 wherein said polyalkylene glycol is a block copolymer polyol characterized by a molecular weight of about 4750; said block copolymer polyol being obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of about 950. 
     
     
       11. The polyurethane polyether resin of claim 3 wherein said polyalkylene glycol is a block copolymer polyol characterized by a molecular weight of about 7500; said block copolymer polyol being obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of about 2250. 
     
     
       12. The polyurethane polyether resin of claim 3 wherein said polyalkylene glycol is a block copolymer polyol characterized by a molecular weight of about 6510; said block copolymer polyol being obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of about 2250. 
     
     
       13. The polyurethane polyether resin of claim 3 wherein said polyalkylene glycol is a block copolymer polyol characterized by a molecular weight of about 13,333; said block copolymer polyol being obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of about 4000. 
     
     
       14. The polyurethane polyether resin of claim 3 wherein said polyalkylene oxide glycol is polypropylene glycol. 
     
     
       15. The polyurethane polyether resin of claim 3 wherein said polyisocyanate is methylene di(cyclohexylisocyanate). 
     
     
       16. The polyurethane polyether resin of claim 3 wherein said polyalkylene oxide is a polyethylene oxide having a molecular weight in the range of 200 to 13,333. 
     
     
       17. A polyurethane polyether resin obtained by reacting a mixture of polyethylene glycol, diethylene glycol, delta gluconolactone and methylene di(cyclohexylisocyanate) in the presence of a catalyst. 
     
     
       18. The polyurethane polyether resin of claim 17 obtained by reacting a mixture of about 54.6 parts of polyethylene glycol (M. Wt. 1450), about 8.7 parts of diethylene glycol, about 5.8 parts of delta gluconolactone and about 40.4 parts of methylene di(cyclohexylisocyanate) in the presence of about 0.5 parts dibutyl tin dilaurate. 
     
     
       19. A carrier system comprising an active agent and a hydrophilic polymer as a carrier vehicle therefore, said carrier vehicle comprising a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone. 
     
     
       20. In a method for releasing an active agent in a medium in which said active agent is used the improvement comprising: incorporating said active agent in a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone;   exposing said polyurethane with said active agent to said medium; and   releasing said active agent into said medium at a predetermined rate.   
     
     
       21. The method of claim 20 wherein the medium is water. 
     
     
       22. The method of claim 20 wherein the medium is a body fluid. 
     
     
       23. The method of claim 20 wherein the medium is a gas. 
     
     
       24. The method of claim 23 wherein said gas is air. 
     
     
       25. A photosensitive coating composition comprising an alkaline solution of a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone and a catalyst which accelerates the cross-linking of said resin when exposed to light. 
     
     
       26. The coating composition of claim 25 wherein the catalyst is ammonium dichromate. 
     
     
       27. A photosensitive film comprising a layer of a dichromate catalysed polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone supported on a substrate to which it adheres. 
     
     
       28. A method of protecting and reducing the hydrostatic drag of a surface which comprises applying thereto a coating of a catalysed polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone and exposing said resin coating to light. 
     
     
       29. A hydrostatic drag resistant coating composition comprising an alkaline solution of a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone and a catalyst that accelerates the cross-linking of said resin when exposed to light. 
     
     
       30. The coating composition of claim 29 having present therein an effective amount of an anti-fouling agent. 
     
     
       31. A composition useful in the treatment of burns comprising from about 1 to about 80 parts by weight of polyvinylpyrolidone-iodide and from about 20 to about 99 parts by weight of a polyether polyurethane resin having free hydroxyl and carboxylate groups in the polymer backbone. 
     
     
       32. A burn dressing comprising a film of a polyurethane polyether resin having carboxylate groups and hydroxyl groups in the polymer backbone. 
     
     
       33. A burn dressing comprising a polyurethane polyether resin having carboxylate groups and hydroxyl groups in the polymer backbone, said polyurethane polyether resin being in the form of a finely divided powder. 
     
     
       34. A method of treating burns which comprises applying thereto from solution in a non-toxic solvent a polyurethane polyether resin having carboxylate groups and hydroxyl groups in the polymer backbone.